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The cellular localization of long chain fatty acids in sponges
Abstract
Examination of fractionated sponge tissue shows that long chain fatty acids (LCFAs) occur in high proportions in cell membranes. This conclusion refutes a recent suggestion made by other workers that sponge membranes would contain conventional fatty acids similar to those found in membranes from other organisms.
... Sponges are interesting objects in terms of lipid biochemistry. Bergmann and Swift (1951) were the first to show unusually high quantities of fatty acids in two marine sponges; later on the fatty acid composition of a large number of the marine sponges (Litchfield et al., , 1979Dembitsky and Nebylitsyn, 1980;Dembitsky et al., 1977;Dembitsky and Chelomin, 1985;Morales and Litchfield, 1976;Lawson, 1984;Lawson et al., 1986;Bergquist et al., 1984) as well as freshwater sponges belonging to the class Demospongiae (Dembitsky, 1981b, c) was studied. Sponges contain a large amount of glycolipids (Marsden, 1975) and initially cerebrosides (Vaskovsky et al., 1970;Schmitz and McDonald, 1974;Grode and Cardellina, 1983); the composition of sponge terpenoids (Cimino, 1977;Stonik, 1986;Sliwka et al., 1987), carotenoids (Minale, 1978;Liaaen-Jensen, 1978;Litchfield and Liaaen-Jensen, 1980;Tanaka et al., 1978) and sterols (De Rosa et aL, 1973;Bergquist, 1980;Seldes et al., 1986;Stonik, 1986) were studied. ...
... The FA composition of Antarctic sponges has not been previously reported, nor has the technique been applied for dietary purposes to populations elsewhere in the world. FAA has been applied to sponges for purposes of analyzing biosynthetic pathways (Carlalleira & Pagan 2001), chemotaxonomy (Lawson et al. 1986), and for indicating transfer of symbiotic biomass into sponge cells (Hoffmann et al. 2005). In this regard, the current application of FA results to sponges is novel. ...
Antarctic benthic suspension feeders may consume water column bacteria to buffer the seasonal variation of primary production, yet little is known about consumption of ultraplankton by this fauna. In the present study 3 experiments-fatty acid analysis, stable isotope concentrations, and laboratory-based feeding-addressed the nutritional role of the microbial loop in 4 species of Antarctic sponge: Homaxinella balfourensis, Isodictya setifera, Kirkpatrickia variolosa, and Sphaerotylus antarcticus. Sponges were sampled at distances between 115 and 840 m from the McMurdo Station sewage outfall to investigate local food source variability. The sewage effluent acted as a tracer for particulates larger than bacteria and was identified isotopically and by the biomarker 18:2(n-6). Sponge diets differed between each species: L setifera consumed mostly bacteria, as indicated by the ratio of bacterial fatty acids to polyunsaturated fatty acids; H. balfourensis consumed larger particles, indicated by an abundance of 22:6(n-3) and an outfall signature; K variolosa was intermediate between these two, with abundant 22:6(n-3), but an isotopic signature similar to L setifera. The diet of S. antarcticus was not completely resolved; fatty acid analysis supported its similarity to K, variolosa, yet the isotopic analysis separated it from the other sponges, suggesting that symbionts were abundant enough to confound the results. This study provides the first application of fatty acid analysis to determine diet composition of sponges, the first species-specific stable isotopic analysis of Antarctic sponges, and the first conclusive evidence of differential utilization of microbial loop components by co-occurring sponges.
... Sponges are interesting objects in terms of lipid biochemistry. Bergmann and Swift (1951) were the first to show unusually high quantities of fatty acids in two marine sponges; later on the fatty acid composition of a large number of the marine sponges (Litchfield et al., , 1979 Dembitsky and Nebylitsyn, 1980; Dembitsky et al., 1977; Dembitsky and Chelomin, 1985; Morales and Litchfield, 1976; Lawson, 1984; Lawson et al., 1986; Bergquist et al., 1984) as well as freshwater sponges belonging to the class Demospongiae (Dembitsky, 1981b, c) was studied. Sponges contain a large amount of glycolipids (Marsden, 1975) and initially cerebrosides (Vaskovsky et al., 1970; Schmitz and McDonald, 1974; Grode and Cardellina, 1983); the composition of sponge terpenoids (Cimino, 1977; Stonik, 1986; Sliwka et al., 1987), carotenoids (Minale, 1978; Liaaen-Jensen, 1978; Litchfield and Liaaen-Jensen, 1980; Tanaka et al., 1978) and sterols (De Rosa et aL, 1973; Bergquist, 1980; Seldes et al., 1986; Stonik, 1986) were studied. ...
1.1. Phospholipid composition of the marine sponges belonging to the class Demospongiae was studied.2.2. Content of plasmologen, alkylacyl and diacyl forms in the main classes of glycerophospholipids was established by using the micro-TLC method.3.3. The main components are amino phospholipids; their content in the total lipid extract varies from 20 to 70%.4.4. An unusual lipid composition of the marine sponge phospholipids is discussed.
... Examination of fractionated sponge Halichondria moorei (Lawson et al., 1986) tissue shows that demospongic acids occur in high proportions in cell membranes, Reniera sp. and Pseudaxinyssa sp. (Lawson et al., 1988), and membranes display classical trilaminar structure in four marine and in freshwater sponge Ephydatia mülleri (Lethias et al., 1983). ...
Lipid and phospholipid compositions of an endemic deep-water freshwater gammarid, belonging to the subphylum Crustacea, Acanthogammarus grewingkii was studied. Content of alkenylacyl, alkylacyl and diacyl forms in the main phospholipid classes (phosphatidylethanolamine and phosphatydilcholine) were established using reaction micro-thin-layer chromatography. The fatty acids compositions of total lipids, neutral, glyco- and phospholipid fractions were investigated by capillary gas chromatography-mass spectrometry. Seventy-nine fatty acids were identified: 26 saturated (iso-, anteiso- and cyclo-), 26 monoenoic, 7 dienoic, 14 trienoic and 16 tetra-, penta- and hexaenoic. A number of demospongic fatty acids, such as 5,9–25:2, 5,9,19–26:3, 5,9,17–26:3, 5,9,23–28:3 and 5,9,21–28:3 acids, were found.
... Examination of fractionated sponge Halichondria moorei (Lawson et al., 1986) tissue shows that demospongic acids occur in high proportions in cell membranes, Reniera sp. and Pseudaxinyssa sp. (Lawson et al., 1988), and membranes display classical trilaminar structure in four marine and in freshwater sponge Ephydatia mülleri (Lethias et al., 1983). ...
More than 100 novel, unusual and rare fatty acids, lipids and sterols have been isolated from freshwater sponges. The structures, biogenesis, synthesis and bioactivity of some lipid compounds of freshwater sponge species are reviewed.
... A very small percentage of bacteria are cultivable (Amann et al., 1995), which makes culture-based surveys problematic. Several analyses are performed to locate the compounds in the sponge (e.g., Lawson et al., 1986Lawson et al., , 1988Garson et al., 1992Garson et al., , 1994Faulkner et al., 1994;Unson et al., 1994;Bewley et al., 1996;Uriz et al., 1996a,b;Marin et al., 1998;Gillor et al., 2000;Turon et al., 2000;Salomon et al., 2001;Richelle-Maurer et al., 2001, 2003. Uncertainty remains whether the localization of the compounds also reveals the location of biosynthesis (Piel, 2004), because compounds found in sponge cells might just be stored there. ...
In addition to their pharmaceutical applications, sponges are an important source of compounds that are used to elucidate classification patterns and phylogenetic relationships. Here we present a review and outlook on chemosystematics in sponges in seven sections: Secondary metabolites in sponges; Further applications of bioactive compound research in sponges; Sponge chemotaxonomy; Pitfalls of sponge chemotaxonomy; The chemotaxonomic suitability of sponge compounds; Potential synapomorphic markers in sponges; and The future of sponge chemotaxonomy.
Los mares ocupan aproximadamente tres cuartas partes de la tierra constituyendo el hábitat de una gran cantidad de especies de flora y fauna. Como parte de los organismos marinos, los phylum bioquímicamente más estudiados son Porífera, Cnidaria y más recientemente Ascomycota, de todos ellos se han aislado e identificado un gran número de compuestos químicos, los cuales han mostrado diferentes tipos de actividades biológicas, principalmente citotóxica, bactericida y antioxidante, entre otras. En esta investigación se estudió la esponja marina Iotrochota birotulata recolectada en Punta Bello-Córdoba en el Caribe colombiano lográndose determinar su perfil lipídico a partir del análisis de los correspondientes espectros de masas de sus compuestos constituyentes, fueron identificados 19 ácidos grasos, los cuales son reportados por primera vez para esta especie. Además fueron identificados 10 esteroles. Se encontraron ácidos grasos con cadenas carbonadas entre C15 y C27, mostrando una amplia diversidad estructural lo cual es característico del phylum porífera. En cuanto a los esteroles se encontraron estructuras principalmente con núcleos Δ5 y Δ7 que son los más abundantes en las esponjas. Se encontró moderada actividad antioxidante en la estabilización del catión radical ABTS+• y baja actividad en la estabilización del radical DPPH•, el mayor valor de inhibición se encontró en el extracto acuoso con un valor de IC50 de 43.9 µg/ml frente al catión radical ABTS+•, mostrando que I. birotulata puede producir compuestos con moderada actividad antioxidante. En el ensayo de actividad insecticida, se encontró afectación larval en los extractos metanólico y acuoso en todas las concentraciones y en todos los tiempos de exposición evaluados frente a Spodoptera frugiperda, también se determinó que estos extractos inducen un efecto antialimentario en las larvas como parte del mecanismo insecticida. Se determinaron las condiciones y los tiempos de exposición óptimos para la mejor eficiencia del ensayo, las cuales fueron de 3 000 µg/ml y 48 h para el extracto metanólico y 2 000 µg/ml y 24 h para el extracto acuoso, respectivamente. En conclusión, los extractos evaluados de I. birotulata mostraron moderada actividad antioxidante y buenas e interesantes actividades insecticida y antialimentaria.
A common Great Barrier Reef sponge, previously attributed to the genus Spongia, is described as new and placed in a new genus Rhopaloeides. This genus includes Spongiidae otherwise identical to Spongia in which the cored primary fibres form simple fascicles. The genus is also characterized by its form (massive, thick broad-based lamellae or multiple fused thick clubs). The chemistry is distinctive, characterised by possession of a rare group of C 20 diterpene furanodiols, triols and their peracetates. Considerable variation in the total yield and composition of the diterpenes for different collections of R. odorabile was confusing and led to a suggestion that more than one species was represented. Field experiments in which fragments of one individual sponge were transplanted to different conditions of illumination and depth, demonstrate that the chemical variability reflects the range of environmental conditions under which R. odorabile lives rather than any genetic differences.
The structures of seven minor metabolites, (5)-(11), from the encrusting sponge Cacospongia sp. Were deduced by 1H, 13C and mass spectrometric data. Compounds (5)-(7) are hydroxy derivatives of the previously isolated tribromocacoxanthene (1); their relative stereochemistry was determined from 1H-1H coupling information. Compounds (8)-(11) represent an alternative cyclization mode of a cyclocymopol-related precursor (15) and possess a spiro-fused bicyclic ring system; the relative stereochemistry of (8)-(10) was deduced by 1H n.O.e. difference spectroscopy. The biological role of brominated meroterpenoids in Cacospongia sp. is discussed.
Fatty acids of eight lichen species belonging to the genus Cladonia were examined by GC-MS. Twenty-two saturated, 23 monoene, five diene, nine triene and eight tetra-, penta- and hexaene fatty acids were identified. Unusually for lichens, very long-chain fatty acids, 25:1, 26:0, 26:1, 26:3, 28:0, 28:1, and 30:1 were detected.
As reported earlier, the marine sponge phospholipids 1,2-di-5,9-hexacosadienoyl-sn-glycero-3-phosphocholine (PC: (26 : 2, 26 : 2)) and its phosphoethanolamine counterpart exclude cholesterol to a great extent from their liposomal bilayers. To understand the reason for this exclusion, shorter acyl chain analogs of these phospholipids were synthesized. Liposomes composed of PC (18 : 2, 18 : 2), PC (22 : 2, 22 : 2) or PC (24 : 2, 24 : 2), with the unique Δ5,9 unsaturation typical of sponge phospholipids, incorporated cholesterol Δ5,9-PE (24 : 2, 24 : 2) which also incorporated cholesterol, had a phase transition temperature identical to its PC counterpart. Differential scanning calorimetry indicated that Δ5,9-PC (26 : 2, 26 : 2) could incorporate 1-stearoyl-2-oleoyl-sn-glycerophosphocholine PC (18 : 0, 18 : 1) into its bilayers at various ratios (20, 40, 60, 80 mol%), but part of PC (18 : 0, 18: 1) displayed monotectic behavior. When 20 mol cholesterol was added to thesemixtures, the sterol interacted preferentially with the PC (18 : 0, 18 : 1) but was also incorporated in all ratios into the mixture of phospholipids and created one major transition endotherm.
The 14C-labeled short-chain fatty acid 10-methylhexadecanoic acid (10-Me-16:0) as well as its hitherto undescribed 10R and 10S antipodes was incorporated into the marine sponge Aplysina fistularis and transformed in situ into 22-methyl-5,9-octacosadienoic acid (22-Me-Δ 5,9-28:2) by chain elongation. No qualitative specificity between the two enantiomers was observed. [ 3H]Methionine was also incorporated into the sponge to investigate the methylation process; a rapid incorporation into the short branched fatty acids occurred with subsequent chain elongation. Both enantiomers were synthesized starting from (+)-pulegone to determine the absolute configuration of the 22-methyl-5,9-octacosadienoic (22-Me-Δ 5,9-28:2) acid. The naturally occurring acid has the 22R configuration.
The differing sponge and symbiotic microbial cell types in the tropical marine spongeAmphimedon sp. were fractionated according to density, investigated by electron microscopy, and analyzed by high-performance liquid
chromatography and nuclear magnetic resonance for the presence of the terpene metabolite diisocyanoadociane (1) and Δ5,7-sterols (2–7). A sample of whole sponge was dissected into superficial ectosome and deeper choanosome. The superficial tissue
was found to be enriched in sterol relative to choanosome; however, extracts from both tissues contained terpene. Dissociation
of whole sponge followed by Ficoll density gradient fractionation showed that there are two chemically distinct types of sponge
cells inAmphimedon sp.—small non-nucleolated cells of low density contain terpene 1 together with sterols, while larger nucleolated cells contain
significant levels of terpene, but only traces of sterol. Membrane fractionation studies were undertaken to establish whether
the terpene components were located specifically in the cell membranes of these two cell types. A membrane vesicle pellet
spun down at 100,000×g from small sponge cells contained sterols, but only traces of terpene, whereas the membrane vesicle preparation from heavier
cells contained both terpenes and sterols. Subsequently, the presence of terpenes together with sterols was demonstrated in
a membrane vesicle preparation of purity >90% prepared from bacteria-free sponge cells. These results provide the first experimental
evidence that terpenes are associated with sponge cell membranes, where they may function as structural components.
The composition of the lipophylic extract from the sponge Ircinia
muscarum and its cell cultures developed under light and dark conditions was investigated. Lipids and their fatty acids, as well as volatile compounds and sterols, were identified. The differences between the two cell cultures did not appear to be very significant, while there were significant differences between the sponge and the cell cultures. Most of the isolated compounds were found for the first time in dictyoceratide sponges.
Lipids and phospholipids (both plasmalogen and alkyl forms) of the freshwater sponge Lubomirskia baicalensis and the sponge's gammarid parasite Brandtia (Spinacanthus) parasitica were examined. Composition of alkenyl-acyl (plasmalogen), alkylacyl and diacyl forms of major phospholipid classes, phosphatidylethanolamine and phosphatidylcholine were determined. One hundred and eighty-three fatty acids were identified by GC-MS: 46 saturated, 55 monoenoic, 35 dienoic, 25 trienoic and 22 tetra-, penta- and hexaenoic. The freshwater sponges, belonging to the family Lubomirskiidae, were shown to contain unusual long-chain fatty acids: anteiso-5, 9–28:2, branched-5, 9–29:2, 5,9,23–29:3, 5,9,23–30:3, 15,18,21,24–30:4 and 15,18,21,24,27–30:5. Some from these fatty acids were found in lipids of the amphipod parasite.
1.1. Phospholipids of the freshwater sponge Euspongilla lacustris from the Volga river estuary were examined.2.2. The freshwater sponges belonging to the family Spongillidae were shown to contain demospongic fatty acids.3.3. Composition of fatty acids in phospho-, glyco- and neutral lipid fractions was studied.
The composition of the lipophylic extract from the sponge Suberites domuncula was investigated. Lipids and their fatty acids, as well as volatile compounds and sterols were identified. Stanols are the main class of steroids in the investigated sponge. A high concentration of unsaturated long chain fatty acids (C26C28) was identified. The presence of branched and odd fatty acids indicates associated bacteria in the sponge.
1. The phospholipid fatty acid compositions of the sponges Ircinia strobilina, Ircinia felix, Ircinia campana, Ircinia sp., Spongia tubulifera and Dysidea etherea were studied, revealing the presence, besides other common fatty acids, of considerable amounts (2-5%) of the novel 23-methyl-5,9-tetracosadienoic acid (1). 2. The demospongic acids 5,9-tetracosadienoic acid, 23-methyl-5,9-tetracosadienoic acid (1), and 5,9-pentacosadienoic acid, were particularly abundant in sponges of the genus Ircinia, in contrast to the most common 5,9-hexacosadienoic acid found in other species. These findings are discussed in terms of the taxonomy of the Dictyoceratida. 3. The complete characterization of the novel phospholipid fatty acid 23-methyl-5,9-tetracosadienoic acid (1) is presented.
Analyses of fatty acids with carbon numbers between C12 and C22 are reported for five Great Barrier Reef sponges. These analyses indicate that phototrophic cyanobacterial symbionts (blue-green algae) present in three of the sponges are chemically distinct, whereas the other two sponges do not contain cyanobacterial symbionts. All the sponges contain other, nonphototrophic bacteria. The fatty acid analyses indicate that the non-phototrophic bacterial populations present in the different sponges are distinct in both their chemical compositions and their abundances. Nonphototrophic bacteria are estimated to account for between 60 and 350 micrograms/g (extractable fatty acids:tissue wet weight), whereas cyanobacteria account for between 10 and 910 micrograms/g. One sponge (Pseudaxinyssa sp.) contains a relatively large amount of the isoprenoid acid, 4, 8, 12-trimethyltridecanoic acid; this acid is presumed to be derived from phytol, a degradation product of chlorophyll. This sponge also contains relatively large amounts of the nonmethylene interrupted fatty acid, octadeca-5,9-dienoic acid. Analyses of interior and cyanobacteria-rich surface tissues of this sponge indicate that these two acids are probably not associated with the symbiotic cyanobacteria.
Subcellular fractionation by differential centrifugation was performed on two previously unstudied marine sponges that predominantly contain either conventional (Reniera sp.) or unconventional (Pseudaxinyssa sp.) sterols. Direct evidence for the presence of unconventional sterols with C24 alkylated side chains in the cellular membranes of Pseudaxinyssa sp. is provided, but the presence of unconventional sterols in sponge membranes is shown not to be a universal feature of the Porifera. Possible structural and functional roles of unconventional lipid molecules in sponge cell membranes are discussed.
Subcellular fractionation by differential centrifugation was performed on two previously unstudied marine sponges (Reniera sp. and Pseudaxinyssa sp.) that represent both major subclasses of the Demospongiae. Long chain fatty acids (LCFA) with 24-30 carbon units were found as major constituents of cell membrane isolates of both sponges. Most LCFA were polyunsaturated and were constituents of the phospholipids, which are typical membrane lipids, and in particular the amino-phospholipids. The LCFA composition of phospholipids from whole sponge tissue was shown to provide a reliable indication of the LCFA composition of cell membrane phospholipids in the sponges studied. An unusual triply branched C16 isoprenoid fatty acid, 4,8,12-trimethyltridecanoic acid, also was identified as a cell membrane acid in the sponge Pseudaxinyssa sp.
The first direct evidence is provided for the presence of unconventional lipids in a particular subcellular membrane system of a sponge. Spherulous cells were isolated from the variety of cell types present in the marine sponge Aplysina fistularis by density gradient centrifugation. Spherulous cell plasma membrane was subsequently isolated by cell rupture followed by differential centrifugation and sucrose, or Percoll, density gradient ultracentrifugation. Plasma membrane isolates were identified and assessed for purity using [3H]concanavalin A plasma membrane marker, sodium dodecyl sulfate polyacrylamide gel electrophoresis and ratios of protein, sterol and phosphate. Plasma membrane isolates could not be assessed for purity by traditional enzymatic means. Spherulous cell plasma membrane was found to contain unusual lipids, including long-chain (C24-C30) fatty acids (16.8-27.2%) and unconventional 26-alkylated sterols (66.4-72.6%), in addition to more conventional fatty acids and sterols. Spherulous cell intracellular membranes were also found to contain long-chain fatty acids and unconventional sterols, although the relative importance of these unusual lipids apparently varies between intracellular membranes, with some containing approximately 50% long-chain acids.
The tropical marine sponge Amphimedon terpenensis (family Niphatidae, order Haplosclerida) has previously been shown to possess unusual lipids, including unusual fatty acids. The biosynthetic origin of these fatty acids is of interest as the sponge supports a significant population of eubacterial and cyanobacterial symbionts. The total fatty acid composition of the sponge was analyzed by gas chromatography/mass spectrometry of the methyl esters. Among the most abundant of the fatty acids in intact tissue were 16:0, 18:0 and 3,7,11,15-tetramethyl-hexadecanoic (phytanic) acid. In addition, three brominated fatty acids, (5E,9Z)-6-bromo-5,9-tetracosadienoic acid (24:2Br), (5E,9Z)-6-bromo-5,9-pentacosadienoic acid (25:2Br) and (5E,9Z)-6-bromo-5,9-hexacosadienoic acid (26:2Br) were also present. The three brominated fatty acids, together with phytanic acid, were isolated from both ectosomal (superficial) and choanosomal (internal) regions of the sponge. Analysis of extracts prepared from sponge/symbiont cells, partitioned by density gradient centrifugation on Ficoll, indicated that phytanic acid and the three brominated fatty acids were associated with sponge cells only. Further, a fatty acid methyl ester sample from intact tissue of A. terpenensis was partitioned according to phospholipid class, and the brominated fatty acids were shown to be associated with the phosphatidylserine and phosphatidylethanolamine fractions that are commonly present in marine sponge lipids. The phosphatidylcholine and phosphatidylglycerol fractions were rich in the relatively shorter chain fatty acids (16:0 and 18:0). The association of brominated long-chain fatty acids (LCFA) with sponge cells has been confirmed. The findings allow comment on the use of fatty acid profiles in chemotaxonomy and permit further interpretation of LCFA biosynthetic pathways in sponges.(ABSTRACT TRUNCATED AT 250 WORDS)
Acholeplasma laidlawii cells grown with oleic acid produced much more colored carotenoids than did cells grown with elaidic acid. The amount of carotenoids was decreased 80 to 90% by growing the cells with 0.05 M propionate, resulting in a marked increase in the mobility of both 5-doxylstearate and 12-doxylstearate incorporated into the membranes. The fatty acid composition of the propionate-grown cells differed from that of cells grown without propionate by containing odd-numbered rather than even-numbered saturated fatty acids, but the ratios of saturated to unsaturated fatty acids were the same. To determine whether the carotenoids are the cause for the restricted mobility in the membranes, the carotenoids were selectively removed from A. laidlawii membranes by incubating the membranes with phosphatidylcholine vesicles. The carotenoid-depleted membranes showed an increase in the mobility of the hydrocarbon chains of the spin-labeled fatty acids. Furthermore, the incorporation of carotenoids into artificial membrane vesicles restricted the mobility of the hydrocarbon chain. Our results support the notion that the carotenoids in A. laidlawii act as a rigid insert reinforcing the membrane bilayer.
Fats and oils provide the most concentrated source of energy in the diet, about 9 kcal/g. Animal tissues, dairy products, and oils extracted from certain seeds contribute most of the fat in the diet (see Table I). The source, chemical nature, and processes that fats and oils are subjected to before they reach the market shelf are important aspects of the study of lipids. A fat is distinguished from an oil by its solid state at a particular temperature, usually room temperature. Some oils are winterized to remove triglycerides that would cause the oil to solidify in the refrigerator; other oils are lightly hydrogenated to convert highly unsaturated fatty acids to more saturated acids to prevent the development of off-flavors and rancidity.
A novel fatty acid, (2,21)-2-methoxy-21-octacosenoic acid, was shown to be present in the phospholipids of the sponge .
The marine spongeChondrilla nucula contains 34% 30∶3Δ5,9,23 in its total fatty acids. This nonmethylene-interrupted polyunsaturated acid, unknown in other living
organisms, occurs mainly as an ester in phosphatidylethanolamine.
The fatty acyl components of the phospholipids from the spongePetrosia ficiformis consisted predominantly of branched, especially iso and anteiso acids. The two major components of the complex mixture are the hitherto unknown Z,Z-25-methyl-5,9-hexacosadienoic and Z,Z-24-methyl-5,9-hexacosadienoic acids. Other unknown acids are: 7,13,16-docosatrienoic acid, 15-methyldocosanoic acid, 15-methyltricosanoic acid and 24-methyl-5,9-pentacosadienoic acid. Short branched-chain fatty acids, presumably of bacterial origin, are considered to be the possible bioprecursors of these novel phospholipid constituents. The major phospholipids were PE, PC, PG, PS and PI. The distribution of fatty acids among the phospholipid classes was also studied.
Twenty genera of sponges from the class Demospongiae have been examined for fatty acid composition. All contain unusually
high levels (34–79%) of C24−C30 fatty acids not generally found in other organisms. These characteristic “demospongic acids” are mostly polyunsaturated.
The marine sponseCliona celata contains 3.5% 30∶4ω6 and 7.0% 30∶5w3 in its total fatty acids. These C30 polyunsaturated structures are unknown in other living organisms. Both acids occur mainly as phosphatidylserine esters.
A systematic search for constituents of marine sponges has yielded over one hundred new compounds, most of them with unique structural features. A broad survey of the field is presented and certain topics, particularly those closely related to recent work done in our own laboratory on sesquiterpenoids, are discussed in more detail.
The component acid mixtures of the lipids from the sponges, Spheciospongia vesparia and Suberites compacta have been investigated. Their most characteristic features are their great complexity and the preponderance of C26- and C28-acids. Palmitic acid and stearic acid have been isolated from the acid mixture obtained from Spheciospongia. The presence in this mixture of unsaturated C24-acids has been demonstrated by their conversion to tetracosanoic acid. A new dienoic acid has been isolated from the mixture of C26-acids. It was identified by its conversion to a tetrabromide and to hexacosanoic acid. Oxidative fission has given results indicating that this acid is Δ17,20-hexacosadienoic acid. The presence of Δ9-hexacosenoic acid has also been demonstrated. Palmitic acid and α-hydroxytetracosanoic acid have been isolated from the acid mixture obtained from Suberites. A new octacosenoic acid has been obtained from the C28-acid fraction of this mixture. It was identified by its conversion to a dibromide and to octacosanoic acid. The presence in the mixture of an octacosatrienoic acid was demonstrated by the isolation of a hexabromoöctacosanoic acid. Glycerol has been isolated from the lipids of both sponges. The significance of these observations has been discussed.
The Demospongiae (Porifera) have yielded a wide range of novel and conventional sterols; a sample of 55 species screened and reported on have yielded 45 distinct sterol structures. The taxonomic relevance of the occurrence of particular sterols or overall sterol complement is evaluated and has proved to be informative in the case of the Verongida, Nepheliospongida, Axinellida and Hadromerida. A possible relationship between the occurrence of 26-methyl sterols and oviparous reproductive patterns within the Ceractinomorpha is noted. Sterol complement is observed to be qualitatively stable despite season and location of collection. High molecular weight sterols, present as major components, are probable membrane constituents. They afford an interesting parallel to the occurrence of diverse, high carbon fatty acids in sponge membranes.
Investigation of the fatty acid profiles of 55 species of Porifera has confirmed the occurrence of high percentages of both long chain fatty acids (C24-C30) and polyunsaturated acids. These features of the fatty acid profile in conjunction with the content of branched chain acids and the dominance of particular acids in different species allow some systematic discussion. The Dictyoceratida, Clathriidae, Halichondrida, Homoscleromorpha and Calcarea are distinguished by aspects of their fatty acid profiles. The diversity in number and type of sponge fatty acids exceeds that of any other phylum. Environmentally induced variation in fatty acid content is such that percentage compositions alone have little taxonomic informational value.
The free sterols and phospholipids of the demospongeAplysina fistularis were isolated and analyzed. The free sterols consisted mainly of the unusual 26-methylated sterols aplysterol (53%) and 24(28)-dehydroaplysterol
(7%) together with 7 commonly occurring sterods. The major phospholipids were phosphatidylcholine, phosphatidylglycerol, phosphatidylinositol,
phosphatidylethanolamine, phosphatidylserine and diphosphatidylglycerol. The major fatty acyl components of the phospholipids
consisted of 85% C14−C20 acids, including the unprecedented 2,6,10-trimethyl-5-tetradecenoic acid and 11-methyloctadecanoic acid. The remaining 15%
were C27−C30 demospongic acids, including 2 novel acids tentatively assigned the structures 5,9,23-octacosatrienoic acid and 5,9,23-nonacosatrienoic
acid, and 3 novel acids proven to be 5,9,21-octacosatrienoic acid, Z,Z-20-methyl-5,9-hexacosadienoic acid and Z,Z-22-methyl-5,9-octacosadienoic
acid. The biosyntheses of the novel demospongic acids are proposed to occur by chain elongation of monoenoic or branched precursors
followed by desaturation. The large quantities of typically bacterial phospholipids and fatty acids found implied the presence
of bacteria in the sponge, in agreement with microscopic studies. Analysis of the phospholipid-bound fatty acids in a sponge
cell-enriched fraction indicated that the demospongic acids, including the 2 branched structures, were the major acids of
the sponge cells. The presence inA. fistularis of demospongic acids containing membrane disordering groups—methyl branches or double bonds—on the ω7 carbon is proposed
to be due to the need by the sponge for membranes possessing fluidity near the middle of the phospholipid bilayer. It is also
proposed that the C26 methyl group of aplysterol causes disordering of the phospholipid bilayer in the same region, and thus also evolved in response
to this need.
1.(1) Complete characterization of the fatty acids of the marine sponge Microdona prolifera, including double bond positional isomers, has identified 95 different acids in amounts of 0.1% or more. Trace amounts of 23 other acids were found.2.(2) 48% of the fatty acids present have C24–C28 chain lengths. These are all saturates, monoenes, dienes and trienes; the tetraene, pentaene and hexaene acids possess the usual C18–C22 carbon chains. The numerous C24–C28 acids present apparently originate within the sponge itself, indicating a highly active chain elongation sytem.3.(3) A new family of C24, C25, C26 and C27 polyunsaturated acids with isolated double bonds has been discovered. All contain Δ5,9 unsaturation. Specific acids identified were 5,9–24:2; 5,9–25:2; 5,9–26:2; 5,9,17–26:3; 5,9,19–26:3; 5,9,19–27:3 and 5,9,20–27:3. Biosynthetic pathways for such acids are proposed, based on intermediates found in our fatty acid analyses.
Whole document restricted, see Access Instructions file below for details of how to access the print copy. The fatty acid content of 30 species of Porifera, including samples of Hexactinellida and Lithistida for which no fatty acid data previously existed, have been examined. Sponges are unique among animal phyla in diversity of fatty acids with generally high levels of LCFAs (C24-30), high unsaturation (mainly polyunsaturation), and high incidence of branched and odd chain fatty acids. Further, peculiarities in the proportions of individual acids of particular chain lengths distinguish the phylum. Hexactinellid fatty acid traits corresponded closely to those of Demospongiae while the calcareous species was atypical in exhibiting comparatively low levels of LCFAs and unsaturation. Seasonal and geographical influences on components of the fatty acid profile limit the extent to which this information can be utilised in a chemotaxonomic sense. The major trends in seasonal variation of fatty acid content were in an increase in the levels of unsaturated fatty acids and a decrease in the levels of LCFAs during winter. The effects were less pronounced in a subtidal than intertidal species and are considered to be related to environmental temperature. LCFAs predominated in the phospholipids but also were present in high amounts in neutral lipids. The major changes in fatty acid content of the total lipid with season were reflected in the fatty acids of the phospholipids. Also, LCFAs were concentrated in cellular membranes of the sponge. Temperature-induced seasonal changes in LCFA and UFA composition could be explained as an attempt to maintain .the membranes from which these acids originate, in an optimal state of physico-chemical function across the environmental temperature range. This interpretation is supported by observation of an increased content of higher melting point lipids in the sponge in summer. The sensitivity of sponge membranes to temperature was demonstrated by thermal-induction of phase separations in membrane lipids. A major phase separation in both isolated lipids and membranes occurred within a ca. 8 °C of the normal growth temperature range of the sponge. It indicated that membrane lipids exist in a fluid state in the living sponge so that any variation in environmental temperature would affect the lipid fluidity of the membrane and hence physiological membrane processes. This also lends support for some control being exerted on the lipid fluidity of sponge membranes. Any such control must be non-behavioural since sponges are poikilotherms. Minor changes in the proportions of different phospholipids with season were indicated and are also likely to affect the physical properties of membranes which contain them. In general, the lipid yield from sponges as a proportion of the total dry weight is highly dependent on the skeletal composition, specifically the ratio of the structural to living tissue. Therefore lipid yield is not a reliable parameter for classifying sponges. The occurrence of terpenoid metabolites has proved more informative taxonomically and characterised those groups with a low sterol content, e.g. Dictyoceratida. A coincidence of occurrence of terpenoids and high levels of C25 of fatty acids was noted.
Derivatives of one triterpene family, the hopane family, are widely distributed in prokaryotes; they may be localized in membranes, playing there the same role as sterols play in eukaryotes, as a result of their similar size, rigidity, and amphiphilic character. Their biosynthesis embodies many primitive features compared to that of sterols and could have evolved toward the latter once aerobic conditions had been established. Membrane reinforcement appears to be achieved in other prokaryotes by other mechanisms, involving either approximately 40-A-long rigid hydrocarbon chains terminated by one polar group acting like a peg through the double-layer or similar chains terminated by two polar groups acting like tie-bars across the membrane. These inserts can be tetraterpenes (e.g., carotenoids). The biophysical function of membrane optimizers appears to have evolved toward sterols by changes limited to only a few enzymatic steps of the same fundamental biosynthetic processes.
Membranes are proposed to consist of a hydrophobic core, two hydrogen belts, and two polar zones. The hydrogen belts consist
of hydrogen bond acceptors, i.e. the carbonyl groups of phospholipids and sphingolipids, and hydrogen bond donors, i.e. the
labile hydrogens of cholesterol, sphingosine, proteins, and water. The density of anhydrous hydrogen bonding and the impermeability
of the membrane increase with increasing concentrations of cholesterol, sphingolipids, α-hydroxy acyl residues, plasmalogens,
and ether phospholipids. Cholesterol owes its membrane-closing properties to its rigid longitudinal orientation in the membrane
combined with the latitudinal orientation of the O−H bond. It is suggested that the intrinsic proteins of membranes are held
in position by hydrogen bonding, as well as by hydrophobic and electrostatic forces, and that hydrogen bonding also mediates
the penetration of membranes by proteins.
Some recent evidence limits possible models for the interaction. (1) Differential scanning calorimetric measurements6 show that as the cholesterol content of phospholipid-chole-sterol bilayers increases, the heat absorbed in the gel to liquid crystal phase transition8 decreases until no transition is observed.
Sterols, or in rare cases structurally similar molecules, are biosynthesized or at least required by all eucaryotic organisms,
as well as by many procaryotic ones, regardless of their status as plants, animals, or protista. This information, together
with quantitative, structural, metabolic, and other data is reviewed. It is interpreted to mean that the primary role sterols
play in nature is a nonmetabolic one as architectural components of membranes and that this role can be played, but less well,
by other molecules which approximate the steroidal structure. The biosynthetic process should, therefore, and actually does
not appear to be correlatable with this role, which, in turn, is correlatable with phylogenesis. The Δ24-reduction-alkylation bifurcation, for instance appears to be interrelated profoundly with the evolutionary differentiation
of the animal from the plant kingdom.
Fatty acid analysis of the total lipids from the marine spongeMicrociona prolifera by gas liquid chromatography on an EGSS-X column revealed two major peaks with equivalent chain length values of 27.08 and 27.74. Each of these components was isolated as a separate band by thin layer chromatography on AgNO3-silicic acid. Characterization of the two unknowns by IR spectroscopy, NMR, hydrogenation, and gas liquid chromatography revealed that the unknown acids weren-26∶2 andn-26∶3 containing only nonmethylene interruptedcis-double bonds. Reductive ozonolysis identified the 26∶2 ascis-5,cis-9-hexacosadienoic acid and the 26∶3 ascis-5,cis-9,cis-19-hexacosatrienoic acid. Analysis of the fatty acid composition ofMicrociona total lipids showed 14% 26∶2 and 31% 36∶3. The neutral lipids, phosphatidylethanomaline, and phosphatidylserine all contained >41% C26 acids; but only 4% C26 was present in the phosphatidylcholine.
Freeze-fracture replicas of sponge cell membranes revealed in general a low density of intramembranous particles, with the exceptions of the membrane (silicalemma) surrounding the siliceous spicules in Ephydatia and the membranes of spherulous cells in Chondrosia. In addition, several types of particle arrangements were observed. A classical necklace is present at the base of the choanocyte flagellum. Rosettes of particles are particularly obvious in the apical membranes of choanocytes, where they are associated with the fuzzy coat covering these cells. Parallel ridges of particles were observed along the microvilli of the choanocyte collar, at sites of insertion of connecting filaments. Rows of particles were observed in the plasma membrane of pinacocytes in Ephydatia where they are located on areas deformed by protruding fibrillar inclusions. Pinacocyte plasma membranes in this species also can contain accumulations of particles which are likely related to desmosomes. Single rows of aligned particles and double rows of staggered particles (sometimes organized in large plates) in addition to rhombic particle arrays were encountered on replicas of marine sponge cell membranes. No classical arrangements corresponding to gap junctions, tight junctions or septate desmosomes were observed. The significance of these data is analysed.
Fatty acid composition of freshwater sponges of the class Demospongiae. I. Genus Lubomirskia
- Dembitskii
Lipids of marine origin. I. Unusual lipid from Halichondria panicea sponge
- Demhitskii
Fatty acid composition of freshwater sponges of the class Demospongiae. II. Genera Swartschewskia and Baikalospongia
- Dembitskii
Lipids of sea origin—II. The comparative research of phospholipid and fatty acid composition of sea sponges from the Japanese sea
- Dembitskii